CN118126262B - Preparation method and application of organosilicon toughening agent - Google Patents
Preparation method and application of organosilicon toughening agent Download PDFInfo
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- CN118126262B CN118126262B CN202410537101.6A CN202410537101A CN118126262B CN 118126262 B CN118126262 B CN 118126262B CN 202410537101 A CN202410537101 A CN 202410537101A CN 118126262 B CN118126262 B CN 118126262B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 32
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- OHOPKHNWLCMLSW-UHFFFAOYSA-N pinoresinol Natural products C1=C(O)C(OC)=CC(C2C3C(C(OC3)C=3C=C(CO)C(O)=CC=3)CO2)=C1 OHOPKHNWLCMLSW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000007221 pinoresinol Nutrition 0.000 claims abstract description 25
- BURBOJZOZGMMQF-UHFFFAOYSA-N xanthoxylol Natural products C1=C(O)C(OC)=CC=C1C1C(COC2C=3C=C4OCOC4=CC=3)C2CO1 BURBOJZOZGMMQF-UHFFFAOYSA-N 0.000 claims abstract description 25
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- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 24
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 24
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 20
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 20
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 20
- ZIWRUEGECALFST-UHFFFAOYSA-M sodium 4-(4-dodecoxysulfonylphenoxy)benzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccc(Oc2ccc(cc2)S([O-])(=O)=O)cc1 ZIWRUEGECALFST-UHFFFAOYSA-M 0.000 claims abstract description 20
- -1 cyclic siloxane Chemical class 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims abstract description 13
- 229920000053 polysorbate 80 Polymers 0.000 claims abstract description 13
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims abstract description 12
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims abstract description 10
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 10
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 claims abstract description 10
- CADZRPOVAQTAME-UHFFFAOYSA-L calcium;hydroxy phosphate Chemical compound [Ca+2].OOP([O-])([O-])=O CADZRPOVAQTAME-UHFFFAOYSA-L 0.000 claims abstract description 10
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims abstract description 10
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- NRTJGTSOTDBPDE-UHFFFAOYSA-N [dimethyl(methylsilyloxy)silyl]oxy-dimethyl-trimethylsilyloxysilane Chemical compound C[SiH2]O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C NRTJGTSOTDBPDE-UHFFFAOYSA-N 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 7
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 claims description 7
- 235000011056 potassium acetate Nutrition 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 235000002639 sodium chloride Nutrition 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 4
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- 239000000047 product Substances 0.000 abstract description 13
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- 238000013329 compounding Methods 0.000 abstract description 2
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 19
- 229910052710 silicon Inorganic materials 0.000 description 19
- 239000010703 silicon Substances 0.000 description 19
- 239000004417 polycarbonate Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 5
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- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 description 2
- VJXUJFAZXQOXMJ-UHFFFAOYSA-N D-1-O-Methyl-muco-inositol Natural products CC12C(OC)(C)OC(C)(C)C2CC(=O)C(C23OC2C(=O)O2)(C)C1CCC3(C)C2C=1C=COC=1 VJXUJFAZXQOXMJ-UHFFFAOYSA-N 0.000 description 2
- DSCFFEYYQKSRSV-KLJZZCKASA-N D-pinitol Chemical compound CO[C@@H]1[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@H]1O DSCFFEYYQKSRSV-KLJZZCKASA-N 0.000 description 2
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- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a preparation method and application of an organosilicon toughening agent, which belongs to the technical field of high polymer auxiliary agents, wherein the organosilicon toughening agent takes cyclic siloxane monomer, polycaprolactone, diallyl maleate, amino-terminated polyethylene glycol, dodecylbenzene sulfonic acid and Tween 80 as raw materials, and polyvinylpyrrolidone and pinoresinol are added in the mixing process of the raw materials, so that the toughening effect of subsequent reaction products can be improved well, and the organosilicon toughening agent has crack resistance; then mixing the product with sodium dodecyl diphenyl ether disulfonate, methyl acrylate, sodium persulfate and cumene hydroperoxide to prepare a product, and then compounding the product with calcium hydroxy phosphate, benzoyl peroxide, pinoresinol and ethyl methacrylate, wherein the obtained toughening agent has good toughness, greatly improves the toughening effect on plastic materials, particularly low-temperature toughness, and can reduce the dosage of the toughening agent.
Description
Technical Field
The invention belongs to the technical field of high molecular assistants, and particularly relates to a preparation method and application of an organosilicon toughening agent.
Background
Most polymeric plastic articles are brittle at room temperature, thus greatly reducing the useful life and value of the plastic article. If it is desired to improve the brittleness of the plastic article and to give the plastic article better toughness, it is desirable to add a toughening agent, also known as an impact modifier. Currently, the toughening agents are divided into active toughening agents and inactive elastic toughening agents, wherein the active toughening agents refer to active groups which can react with matrix resin on molecular chains of the active toughening agents, and the active toughening agents can form a network structure and increase a part of flexible chains, so that the impact resistance of polymer materials is improved; the non-active toughening agent can have good compatibility with matrix resin, but does not participate in chemical reaction.
The existing toughening agents have a plurality of types, and the toughening effects for different polymers are different. The organic silicon toughening agent is one of the organic silicon toughening agents and has excellent elasticity, however, most of the existing organic silicon toughening agents are prepared by emulsion polymerization, and acrylic ester, methacrylic ester, isooctyl acrylate and the like can be added to improve the performance of the organic silicon toughening agent, but most of the organic silicon toughening agents at present have the problems of poor weather resistance, poor temperature stability and poor anti-dripping property after being added to prepare polymer plastic products, and also indirectly cause poor toughening effect and short service life.
Disclosure of Invention
The organic silicon toughening agent aims at solving the problems of poor weather resistance, poor temperature stability and poor dripping resistance of the existing organic silicon toughening agent after being added and used for preparing polymer plastic products, and can indirectly cause poor toughening effect and short service life. The invention provides a preparation method and application of an organosilicon toughening agent, which takes cyclic siloxane monomer, polycaprolactone, diallyl maleate, amino-terminated polyethylene glycol, dodecylbenzene sulfonic acid and tween 80 as raw materials, and polyvinylpyrrolidone and pinoresinol are added in the mixing process of the raw materials, so that the toughening effect of subsequent reaction products can be improved well, and the toughening agent has crack resistance; then mixing the product with sodium dodecyl diphenyl ether disulfonate, methyl acrylate, sodium persulfate and cumene hydroperoxide to prepare a product, and then compounding the product with calcium hydroxy phosphate, benzoyl peroxide, pinoresinol and ethyl methacrylate, wherein the product obtained after the reaction has good toughness, the toughening effect on plastic materials is greatly improved, and the dosage of a toughening agent can be reduced. The specific technical scheme is as follows:
a preparation method of an organosilicon toughening agent comprises the following steps:
step 1: 400-600 parts of cyclic siloxane monomer, 50-100 parts of polycaprolactone, 50-100 parts of diallyl maleate, 10-30 parts of amino-terminated polyethylene glycol, 3-8 parts of dodecylbenzenesulfonic acid, 3-8 parts of tween 80 and 650-800 parts of water by mass, and mixing to prepare emulsion A; heating the emulsion A to 80-90 ℃, adding 10-30 parts of polyvinylpyrrolidone and 5-10 parts of pinoresinol, and stirring for reaction to obtain emulsion B;
Step 2: according to the parts by weight, 500-800 parts of emulsion B is taken, 5-15 parts of sodium dodecyl diphenyl ether disulfonate is added, mixed, heated to 70-80 ℃, then 100-150 parts of methyl acrylate, 3-8 parts of sodium persulfate and 1-5 parts of cumene hydroperoxide are added, and stirred for reaction, thus obtaining emulsion C;
Step 3: mixing 200-300 parts of water, 2-5 parts of calcium hydroxy phosphate, 1-3 parts of benzoyl peroxide, 1-3 parts of pinoresinol and 40-50 parts of ethyl methacrylate according to parts by weight, heating to 75-90 ℃, adding 60-80 parts of emulsion C, and stirring for reaction to obtain emulsion D;
Step 4: adding demulsifier into emulsion D to cure for 1-2 h, centrifuging, drying under negative pressure, freeze-drying, and pulverizing to obtain organosilicon toughening agent.
In the step 1 of the preparation method, the cyclic siloxane monomer is a mixture of hexamethylcyclotrisiloxane and octamethyltetrasiloxane= (3-6) and (0.5-2) according to mass ratio.
In the step 1 of the preparation method, the mixing rotating speed is 600 r/min-800 r/min, and the time is 30 min-60 min; the rotation speed of the stirring reaction is 200 r/min-300 r/min, and the time is 6 h-8 h.
In the step 2 of the preparation method, the mixing rotating speed is 400-500 r/min, and the mixing rotating speed is 10-20 min; the rotation speed of the stirring reaction is 100 r/min-250 r/min, and the time is 2 h-4 h.
In the step 3 of the preparation method, the rotating speed of the mixing is 600-800 r/min, and the time is 30-60 min.
In the step 3 of the preparation method, the rotation speed of the stirring reaction is 100 r/min-250 r/min, and the time is 3 h-5 h.
In the step 4 of the preparation method, the adding amount of the demulsifier is 0.05 g/L-0.3 g/L emulsion D.
In the step 4 of the preparation method, the demulsifier is a mixture of sodium chloride, potassium acetate, ammonium sulfate= (2-5)/(1.5-2.5)/(1-1.5) according to mass ratio.
In the step 4 of the preparation method, the temperature of the negative pressure drying is below 65 ℃; the median particle size of the pulverization is 10-30 μm.
The organic silicon toughening agent prepared by the preparation method of the organic silicon toughening agent is applied to toughening of plastics.
Compared with the prior art, the preparation method and the application of the organosilicon toughening agent have the beneficial effects that:
1. the organosilicon toughening agent takes cyclic siloxane monomer, polycaprolactone, diallyl maleate, amino-terminated polyethylene glycol, dodecylbenzene sulfonic acid and tween 80 as raw materials, wherein the tween 80 is an emulsifier selected according to the nature and the proportion of the raw materials, so that good mixing and emulsifying effects can be achieved, and the homogeneity of the material is improved. The polyvinylpyrrolidone and pinoresinol are added in the mixing process of the raw materials, so that the toughening effect of the subsequent reaction products can be improved well, and the anti-cracking performance is realized.
2. In the invention, emulsion B is mixed with sodium dodecyl diphenyl ether disulfonate, methyl acrylate, sodium persulfate and cumene hydroperoxide to prepare emulsion C, and then the emulsion C is compounded with calcium hydroxy phosphate, benzoyl peroxide, pinoresinol and ethyl methacrylate, and the product obtained after the reaction has good toughness, so that the toughening effect on plastic materials is greatly improved, and the dosage of a toughening agent can be reduced.
3. The invention aims at the characteristics of each reactant to be mixed or stirred at each step, and the reasonable stirring, shearing and time can not damage the structure of the product under the conditions of ensuring uniform mixing and smooth reaction.
4. Because of the addition of special emulsifying agent, polyvinylpyrrolidone and pinoresinol, demulsifier is needed to promote coagulation and increase yield.
The organosilicon toughening agent can well enhance the toughness of plastics, greatly improve the bending strength and the notch impact strength at-25 ℃, effectively reduce the elongation at break, and have no great influence on the tensile strength, the bending modulus and the notch impact strength index at 25 ℃. The organosilicon toughening agent obtained by adding polyvinylpyrrolidone and pinoresinol components in proper reaction steps can well improve the toughness of plastics under the low-temperature condition.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the invention is not limited to these examples.
Example 1
A preparation method of an organosilicon toughening agent comprises the following steps:
step 1: according to the parts by weight, 500 parts of cyclic siloxane monomer, 80 parts of polycaprolactone, 70 parts of diallyl maleate, 20 parts of amino-terminated polyethylene glycol, 6 parts of dodecylbenzenesulfonic acid, 5 parts of tween 80 and 710 parts of water, and mixing for 50min at 700r/min to prepare emulsion A; after the emulsion is heated to 85 ℃,20 parts of polyvinylpyrrolidone and 8 parts of pinoresinol are added, and stirring reaction is carried out for 7 hours at the speed of 250r/min, so as to obtain emulsion B;
wherein the cyclic siloxane monomer is a mixture of hexamethylcyclotrisiloxane and octamethyltetrasiloxane=5:1 according to mass ratio;
step 2: according to the parts by weight, 600 parts of emulsion B is taken, 10 parts of sodium dodecyl diphenyl ether disulfonate is added, 450r/min is mixed for 15min, the temperature is raised to 75 ℃, then 120 parts of methyl acrylate, 5 parts of sodium persulfate and 3 parts of cumene hydroperoxide are added, and stirring reaction is carried out for 3h at 200r/min, thus obtaining emulsion C;
step 3: according to the parts by weight, 245 parts of water, 3 parts of calcium hydroxy phosphate, 2 parts of benzoyl peroxide, 2 parts of pinoresinol and 45 parts of ethyl methacrylate are mixed for 40min at 700r/min, 70 parts of emulsion C is added after the temperature is raised to 80 ℃, and stirring reaction is carried out for 4h at 200r/min, thus obtaining emulsion D;
Step 4: adding demulsifier into emulsion D according to the ratio of 0.15g/L emulsion D for curing for 1.5 hours, centrifuging, drying at 60 ℃ under negative pressure, freeze-drying, and crushing into the medium-size 22.5 mu m to obtain the organosilicon toughening agent;
Wherein the demulsifier is a mixture of sodium chloride, potassium acetate and ammonium sulfate=3:2:1.2 according to the mass ratio.
The polycaprolactone adopted in the embodiment is polycaprolactone of Hunan semen Junceae New Material Co., ltd., model: PCL-6400; the amino-terminated polyethylene glycol is the amino-terminated polyethylene glycol of the tin-free cloud extraction biotechnology Co., ltd., model: YBST-3; the polyvinylpyrrolidone is polyvinylpyrrolidone PVP K15 of high molecular materials limited company of Shenhua in Huzhou; the sodium dodecyl diphenyl ether disulfonate is sodium dodecyl diphenyl ether disulfonate of the chemical company of cochinc. Hengchang, model: HC2834.
The organic silicon toughening agent prepared by the preparation method of the organic silicon toughening agent is applied to toughening of plastics.
Example 2
A preparation method of an organosilicon toughening agent comprises the following steps:
step 1: 400 parts of cyclic siloxane monomer, 100 parts of polycaprolactone, 50 parts of diallyl maleate, 30 parts of amino-terminated polyethylene glycol, 3 parts of dodecylbenzenesulfonic acid, 8 parts of tween 80 and 650 parts of water, and mixing for 30min at 800r/min to prepare emulsion A; after the emulsion is heated to 90 ℃,10 parts of polyvinylpyrrolidone and 10 parts of pinoresinol are added, and stirring reaction is carried out for 8 hours at 200r/min, so as to obtain emulsion B;
Wherein the cyclic siloxane monomer is a mixture of hexamethylcyclotrisiloxane and octamethyltetrasiloxane=3:2 according to mass ratio;
Step 2: taking 500 parts of emulsion B by mass, adding 15 parts of sodium dodecyl diphenyl ether disulfonate by 400r/min, mixing for 20min, heating to 70 ℃, then adding 150 parts of methyl acrylate, 3 parts of sodium persulfate and 5 parts of cumene hydroperoxide by 100r/min, and stirring and reacting for 4h to obtain emulsion C;
step 3: mixing 200 parts of water, 5 parts of calcium hydroxy phosphate, 1 part of benzoyl peroxide, 3 parts of pinoresinol and 40 parts of ethyl methacrylate for 30min at a speed of 800r/min, heating to 90 ℃, adding 60 parts of emulsion C, and stirring for reacting for 3h at a speed of 250r/min to obtain emulsion D;
Step 4: adding demulsifier into emulsion D according to the ratio of 0.3g/L emulsion D for curing for 1h, centrifuging, drying at 55 ℃ under negative pressure, freeze-drying, and crushing into the medium-size 15.4 mu m to obtain the organosilicon toughening agent;
wherein the demulsifier is a mixture of sodium chloride, potassium acetate and ammonium sulfate=2.5:1.6:1.2 according to the mass ratio.
The polycaprolactone adopted in the embodiment is polycaprolactone of Hunan semen Junceae New Material Co., ltd., model: PCL-6400; the amino-terminated polyethylene glycol is the amino-terminated polyethylene glycol of the tin-free cloud extraction biotechnology Co., ltd., model: YBST-3; the polyvinylpyrrolidone is polyvinylpyrrolidone PVP K15 of high molecular materials limited company of Shenhua in Huzhou; the sodium dodecyl diphenyl ether disulfonate is sodium dodecyl diphenyl ether disulfonate of the chemical company of cochinc. Hengchang, model: HC2834.
The organic silicon toughening agent prepared by the preparation method of the organic silicon toughening agent is applied to toughening of plastics.
Example 3
A preparation method of an organosilicon toughening agent comprises the following steps:
step 1: 400 parts of cyclic siloxane monomer, 50 parts of polycaprolactone, 50 parts of diallyl maleate, 10 parts of amino-terminated polyethylene glycol, 3 parts of dodecylbenzenesulfonic acid, 3 parts of tween 80 and 650 parts of water, and mixing for 30min at 600r/min to prepare emulsion A; after the emulsion is heated to 80 ℃,10 parts of polyvinylpyrrolidone and 5 parts of pinoresinol are added, and stirring reaction is carried out for 6 hours at 200r/min, so as to obtain emulsion B;
Wherein the cyclic siloxane monomer is a mixture of hexamethylcyclotrisiloxane and octamethyltetrasiloxane=3:0.5 according to mass ratio;
step 2: taking 500 parts of emulsion B by mass, adding 5 parts of sodium dodecyl diphenyl ether disulfonate by 400r/min, mixing for 10min, heating to 70 ℃, then adding 100 parts of methyl acrylate, 3 parts of sodium persulfate and 1 part of cumene hydroperoxide by 100r/min, and stirring and reacting for 2h to obtain emulsion C;
Step 3: mixing 200 parts of water, 2 parts of calcium hydroxy phosphate, 1 part of benzoyl peroxide, 1 part of pinoresinol and 40 parts of ethyl methacrylate for 30min at 600r/min, heating to 75 ℃, adding 60 parts of emulsion C, and stirring for reacting for 3h at 100r/min to obtain emulsion D;
Step 4: adding demulsifier into emulsion D according to the ratio of 0.05g/L emulsion D for curing for 1h, centrifuging, drying at 45 ℃ under negative pressure, freeze-drying, and crushing into the medium-size 10 mu m to obtain the organosilicon toughening agent;
wherein the demulsifier is a mixture of sodium chloride, potassium acetate and ammonium sulfate=2:1.5:1 according to the mass ratio.
The polycaprolactone adopted in the embodiment is polycaprolactone of Hunan semen Junceae New Material Co., ltd., model: PCL-6400; the amino-terminated polyethylene glycol is the amino-terminated polyethylene glycol of the tin-free cloud extraction biotechnology Co., ltd., model: YBST-3; the polyvinylpyrrolidone is polyvinylpyrrolidone PVP K15 of high molecular materials limited company of Shenhua in Huzhou; the sodium dodecyl diphenyl ether disulfonate is sodium dodecyl diphenyl ether disulfonate of the chemical company of cochinc. Hengchang, model: HC2834.
The organic silicon toughening agent prepared by the preparation method of the organic silicon toughening agent is applied to toughening of plastics.
Example 4
A preparation method of an organosilicon toughening agent comprises the following steps:
step 1: according to the parts by weight, 600 parts of cyclic siloxane monomer, 50 parts of polycaprolactone, 100 parts of diallyl maleate, 10 parts of amino-terminated polyethylene glycol, 8 parts of dodecylbenzenesulfonic acid, 3 parts of tween 80 and 800 parts of water, and mixing for 60 minutes at 600r/min to prepare emulsion A; after the emulsion is heated to 80 ℃,30 parts of polyvinylpyrrolidone and 5 parts of pinoresinol are added, and stirring reaction is carried out for 6 hours at 300r/min, so as to obtain emulsion B;
Wherein the cyclic siloxane monomer is a mixture of hexamethylcyclotrisiloxane and octamethyltetrasiloxane=6:0.5 according to mass ratio;
Step 2: according to the parts by weight, 800 parts of emulsion B is taken, 5 parts of sodium dodecyl diphenyl ether disulfonate is added, 500r/min is mixed for 10min, the temperature is raised to 80 ℃, then 100 parts of methyl acrylate, 8 parts of sodium persulfate and 1 part of cumene hydroperoxide are added, and the mixture is stirred for 2h at 250r/min to obtain emulsion C;
Step 3: mixing 300 parts of water, 2 parts of calcium hydroxy phosphate, 3 parts of benzoyl peroxide, 1 part of pinitol and 50 parts of ethyl methacrylate for 60min at 600r/min, heating to 75 ℃, adding 80 parts of emulsion C, and stirring for reacting for 5h at 100r/min to obtain emulsion D;
Step 4: adding demulsifier into emulsion D according to the ratio of 0.05g/L emulsion D for curing for 2 hours, centrifuging, drying at a negative pressure below 65 ℃, freeze-drying, and crushing into a median particle size of 24.3 mu m to obtain an organosilicon toughening agent;
wherein the demulsifier is a mixture of sodium chloride, potassium acetate and ammonium sulfate=4.5:2:1.4 according to the mass ratio.
The polycaprolactone adopted in the embodiment is polycaprolactone of Hunan semen Junceae New Material Co., ltd., model: PCL-6400; the amino-terminated polyethylene glycol is the amino-terminated polyethylene glycol of the tin-free cloud extraction biotechnology Co., ltd., model: YBST-3; the polyvinylpyrrolidone is polyvinylpyrrolidone PVP K15 of high molecular materials limited company of Shenhua in Huzhou; the sodium dodecyl diphenyl ether disulfonate is sodium dodecyl diphenyl ether disulfonate of the chemical company of cochinc. Hengchang, model: HC2834.
The organic silicon toughening agent prepared by the preparation method of the organic silicon toughening agent is applied to toughening of plastics.
Example 5
A preparation method of an organosilicon toughening agent comprises the following steps:
Step 1: according to the parts by weight, 600 parts of cyclic siloxane monomer, 100 parts of polycaprolactone, 100 parts of diallyl maleate, 30 parts of amino-terminated polyethylene glycol, 8 parts of dodecylbenzenesulfonic acid, 8 parts of tween 80 and 800 parts of water, and mixing for 60 minutes at 800r/min to prepare emulsion A; after the emulsion is heated to 90 ℃,30 parts of polyvinylpyrrolidone and 10 parts of pinoresinol are added, and stirred for reaction for 8 hours at 300r/min to obtain emulsion B;
Wherein the cyclic siloxane monomer is a mixture of hexamethylcyclotrisiloxane and octamethyltetrasiloxane=6:2 according to mass ratio;
Step 2: according to the parts by weight, 800 parts of emulsion B is taken, 15 parts of sodium dodecyl diphenyl ether disulfonate is added, 500r/min is mixed for 20min, the temperature is raised to 80 ℃, then 150 parts of methyl acrylate, 8 parts of sodium persulfate and 5 parts of cumene hydroperoxide are added, and stirring reaction is carried out for 4h at 250r/min, thus obtaining emulsion C;
Step 3: mixing 300 parts of water, 5 parts of calcium hydroxy phosphate, 3 parts of benzoyl peroxide, 3 parts of pinitol and 50 parts of ethyl methacrylate for 60min at a speed of 800r/min, heating to 90 ℃, adding 80 parts of emulsion C, and stirring for reacting for 5h at a speed of 250r/min to obtain emulsion D;
Step 4: adding demulsifier into emulsion D according to the ratio of 0.3g/L emulsion D for curing for 2 hours, centrifuging, drying at64 ℃ under negative pressure, freeze-drying, and crushing into the medium-size 30 mu m to obtain the organosilicon toughening agent;
Wherein the demulsifier is a mixture of sodium chloride, potassium acetate and ammonium sulfate=5:2.5:1.5 according to the mass ratio.
The polycaprolactone adopted in the embodiment is polycaprolactone of Hunan semen Junceae New Material Co., ltd., model: PCL-6400; the amino-terminated polyethylene glycol is the amino-terminated polyethylene glycol of the tin-free cloud extraction biotechnology Co., ltd., model: YBST-3; the polyvinylpyrrolidone is polyvinylpyrrolidone PVP K15 of high molecular materials limited company of Shenhua in Huzhou; the sodium dodecyl diphenyl ether disulfonate is sodium dodecyl diphenyl ether disulfonate of the chemical company of cochinc. Hengchang, model: HC2834.
The organic silicon toughening agent prepared by the preparation method of the organic silicon toughening agent is applied to toughening of plastics.
Preparation of comparative example 1 silicone toughening agent: no polyvinylpyrrolidone or pinoresinol is added in step 1, and no pinoresinol is added in step 3. Otherwise, the same as in example 1 was conducted.
Preparation of comparative example 2 silicone toughening agent: step 1 does not add dodecylbenzenesulfonic acid and tween 80. Otherwise, the same as in example 1 was conducted.
Preparation of comparative example 3 silicone toughening agent: step 3 does not add pinoresinol and ethyl methacrylate. Otherwise, the same as in example 1 was conducted.
Preparation example PC plastic: 95 parts of polycarbonate, 3 parts of maleic anhydride grafted polyethylene and 2 parts of organosilicon toughening agent (the organosilicon toughening agents of all the embodiments are respectively added), and melting and extrusion molding are carried out to obtain the PC plastic of all the embodiments.
Comparative PC plastic was prepared: 95 parts of polycarbonate, 3 parts of maleic anhydride grafted polyethylene and 2 parts of organosilicon toughening agent (the organosilicon toughening agents of each comparative example are respectively added), and melting and extrusion molding are carried out to obtain PC plastics of each comparative example.
Blank PC plastic was prepared: compared with the PC plastic of the embodiment, the PC plastic of the embodiment is not added with an organosilicon toughening agent and is the same with the PC plastic of the embodiment.
The PC plastic was tested for tensile strength, elongation at break, flexural strength, flexural modulus and notched impact strength, wherein: tensile strength was measured according to GB/T1040.2-2006, test speed: 50mm/min; elongation at break is measured according to GB/T1040.2-2006, test speed: 50mm/min; flexural strength was measured according to GB/T9341-2008; flexural modulus was measured according to GB/T9341-2008; notched impact strength was measured according to GB/T1043.1-2008, spline size: 80mm×10mm×4mm, notch type: type A, test environment 25℃and-25℃respectively. The test results are shown in table 1 below.
TABLE 1 Performance test results
From the above results, it is understood that the tougheners of examples 1 to 5 can well enhance the toughness of PC plastics, greatly improve the bending strength and the notched impact strength at-25 ℃, effectively reduce the elongation at break, and do not greatly affect the tensile strength, the bending modulus and the notched impact strength index at 25 ℃. From comparative example 1, it is evident that the toughness of the composition under low temperature conditions can be improved well by adding a proper amount of polyvinylpyrrolidone and pinoresinol in a proper step, as shown by the decrease in flexural strength and notched impact strength at-25 ℃ and the increase in elongation at break. From comparative example 2, it is known that dodecylbenzenesulfonic acid and tween 80 can well fuse raw materials, so that the reaction is smoother, the product is well homogenized, and the product quality is improved to a certain extent. As is clear from comparative example 3, the addition of pinoresinol and ethyl methacrylate in combination contributes to a reduction in a certain elongation at break and an improvement in notched impact strength at-25 ℃.
Claims (10)
1. The preparation method of the organosilicon toughening agent is characterized by comprising the following steps:
step 1: 400-600 parts of cyclic siloxane monomer, 50-100 parts of polycaprolactone, 50-100 parts of diallyl maleate, 10-30 parts of amino-terminated polyethylene glycol, 3-8 parts of dodecylbenzenesulfonic acid, 3-8 parts of tween 80 and 650-800 parts of water by mass, and mixing to prepare emulsion A; heating the emulsion A to 80-90 ℃, adding 10-30 parts of polyvinylpyrrolidone and 5-10 parts of pinoresinol, and stirring for reaction to obtain emulsion B;
Step 2: according to the parts by weight, 500-800 parts of emulsion B is taken, 5-15 parts of sodium dodecyl diphenyl ether disulfonate is added, mixed, heated to 70-80 ℃, then 100-150 parts of methyl acrylate, 3-8 parts of sodium persulfate and 1-5 parts of cumene hydroperoxide are added, and stirred for reaction, thus obtaining emulsion C;
Step 3: mixing 200-300 parts of water, 2-5 parts of calcium hydroxy phosphate, 1-3 parts of benzoyl peroxide, 1-3 parts of pinoresinol and 40-50 parts of ethyl methacrylate according to parts by weight, heating to 75-90 ℃, adding 60-80 parts of emulsion C, and stirring for reaction to obtain emulsion D;
Step 4: adding demulsifier into emulsion D to cure for 1-2 h, centrifuging, drying under negative pressure, freeze-drying, and pulverizing to obtain organosilicon toughening agent.
2. The method for preparing the organosilicon toughening agent according to claim 1, wherein in the step 1, the cyclic siloxane monomer is a mixture of (0.5-2) of hexamethylcyclotrisiloxane and octamethyltetrasiloxane= (3-6) according to mass ratio.
3. The method for preparing the organosilicon toughening agent according to claim 1, wherein in the step 1, the mixing rotation speed is 600 r/min-800 r/min, and the mixing time is 30 min-60 min; the rotation speed of the stirring reaction is 200 r/min-300 r/min, and the time is 6 h-8 h.
4. The method for preparing the organosilicon toughening agent according to claim 1, wherein in the step 2, the mixing rotation speed is 400 r/min-500 r/min, and the mixing time is 10 min-20 min; the rotation speed of the stirring reaction is 100 r/min-250 r/min, and the time is 2 h-4 h.
5. The method of preparing a silicone toughening agent according to claim 1, wherein in step3, the mixing speed is 600r/min to 800r/min for 30min to 60min.
6. The method for preparing the organosilicon toughening agent according to claim 1, wherein in the step 3, the rotation speed of the stirring reaction is 100 r/min-250 r/min, and the time is 3 h-5 h.
7. The method for preparing the organosilicon toughening agent according to claim 1, wherein in the step 4, the demulsifier is added in an amount of 0.05g/L to 0.3g/L of emulsion D.
8. The method for preparing the organosilicon toughening agent according to claim 1, wherein in the step 4, the demulsifier is a mixture of sodium chloride, potassium acetate, ammonium sulfate= (2-5): (1.5-2.5): (1-1.5) according to mass ratio.
9. The method of preparing an organosilicon toughening agent according to claim 1, wherein in step 4, the temperature of the negative pressure drying is 65 ℃ or lower; the median particle size of the pulverization is 10-30 μm.
10. Use of a silicone toughening agent made using the method of preparation of claim 1 for toughening plastics.
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| CN110452341A (en) * | 2019-09-03 | 2019-11-15 | 铨盛聚碳科技股份有限公司 | A kind of organosilicon toughener and preparation method thereof of emulsion-suspension polymerization synthesis |
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| CN110452341A (en) * | 2019-09-03 | 2019-11-15 | 铨盛聚碳科技股份有限公司 | A kind of organosilicon toughener and preparation method thereof of emulsion-suspension polymerization synthesis |
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